Process and apparatus for continuous treatment of hydrocarbon oil with a. metallic halide



April 21, 1931. R. W .HANNA 1,801,627

PROCESS AND APPARATUS FOR CONTINUOUS TREATMENT OF HYDROCARBON OIL WITH AMETALLIC HALIDE Filed Nov. 27, 1926- corn-ansia caLER REsllmUM LQ31a/vento@ @Hoz new Patented Apr. 21, 1931 UNITEDl STATES PATENTorner-z.

RICHARD W. HANNA, PIEDMONT, CALIFORNIA, A SSIGNOR TO STANDARD OIL COM-PANY Ol' CALIFORNIA, OF SAN FRANCISCO, CALIFORNIA, A CORPORATION OFDELA- WARE' PROCESS AND APPARATUS FOR CONTINUOUS .TREATMENT Ol'HYDROCARBON OIL WITH A METALLIC HALIDE Application led November 27,1928. Serial No. 151,165.

This invention relates tothe treatment of hydrocarbon oils, such aspetroleum o1l, shale oil,or oils` derived from coal or similar sources,with a metallic halide such as alumi- 5 num chloride, and refersparticularly to a coptinuous process of treatlng the-hydrocarbon oilwith a metallic halide.

In the conventional' process of treating hydrocarbon oils with aluminumchloride, the hydrocarbon oils are agitated together in batch lots withaluminum chloride in a reaction chamber in-which heat is supplied to thechamber walls to maintain the desired reaction temperature. In such aprocess, considerable diliiculty is experienced dueto the necessity ofemploying a mechanical agitator inthe reaction chamber. Moreover, theaddition of the greater portion of the heat tothe admixture in thereaction chamber results in unnecessarily large tar or coke formationsand in a poor eicienc of heat transfer. Furthermore, the con ucting ofthe process in batch lots results in a low yield of product from a givensize apparatus.

An object of the present invention is toA provide a process of treatinghydrocarbon oil with alumlnum chloride in which the hydrocarbon oil andaluminum chloride may be continuously agitated together with a con- ,30tinuous conversion of h drocarbon oil to low boiling point oil or naptha and the continuous removal ofl residual aluminum chloride. Another'object of the present invention is to provide a continuous apparatusfor treat- QI ing hydrocarbon oil -withaluminum chloride in which anagitation of the materials may be effected by circulation of liquid fromthe r action chamber back into the reaction chamber entering in the formof Ajets so that the 0 liquid undergoing treatment serves as anagitating means for the mixture. 'By this v method, the process of the.present invention eliminatestheproblems encountered 1n the v lprocessesemploying a mechanical agltatlon 4I of aluminum chloride and hydrocarbonoil together or when the oil agitation is combined with mechanicalagitation substantially simplifies and reduces the mechanical agitatingproblems.'

Another object of the present invention is to provide a process in whicha part, preferably the major part, or final heating of the hydrocarbonoil is conducted in a heating zone separate from the reaction chamber bya continuous circulation of hydrocarbon oil or the liquid admixture fromthe reaction chamber through said heating zone and back into saidagitatin-ggchamber. In this manner, excessive formation of carbon or,coke and high heat losses are avoided. y

Another object of the invention is to pro`- vide a process in which asingle stream of liquid .may be withdrawn from a source of bulk supplyof hydrocarbon oil and aluminum chloride and circulated through aheating zone and back into said bulk supply entering in the form ofagitating jets. The

necessary heat for the reaction is applied largely separate from theagitation chamber andl the heated stream serves as agitating means.

Another object of the present invention is to provide a continuousprocess of treating hydrocarbon oil with aluminum chloride vin whichthere may be circulated from the bulk -supply'of said materials a liquidwhich in its circulating path has separated therefrom Y Vany aluminumchloride compound so that only a substantially. clean stream ofhydrocarbon 'oil passes through the heating zone;

Various further objects and 'advantages of the present invention will beunderstoodl from a description of a preferred form of process andapparatus embodying the invention. For this purpose, reference is madeto the accompanyin drawing in which there is illustrated apre erredexample of an apparatusembodying-the invention, in which i apparatus thepreferred process embodying.A l

the invention may be carried out.

, The drawing represents a diagrammatic view mainly in elevation andpartially in vertical section of thp apparatus.

Referring to the ydrawing, the reaction chamber in which the bulk supplyof materials is maintained is generally indicated at 2. Said reactio'nchamber is preferably an incumbent cylindrical tank. 3 indicates astorage vessel 'or other suitable source of hydrocarbon oil. The storagevessel 3 is indicated as provided with a line 4 including a pump 5 bywhich the hydrocarbon oil may be withdrawn from the storage vessel 3 andpassed into the reaction chamber2. The fresh hydrocarbon oil may bedirectly introduced into the said reaction chamber or into a vapor line6 leading from said reaction chamber.

Preferably the hydrocarbon oil line 4 is connected with the lines 7 and8, the line 7 leading to the upper portion of a dephlegmator or reiuxtower 9 connected with the vapor line 6 and the line 8 leading to acirculating line 1( The circulating line 10 is connected with thereaction chamber at one end, as indicated at 11, and includes a ump 12by which liquid may be withdrawn rom the reaction chamber and forciblycirculated through the heating zone and back' into the chamber.Preferably the heating zone comprises a coil 13 positioned within afurnace 14. The circulating line, 10 also preferably'includes a trap 15between the pump 12 and coil 13 by which any aluminum chloride or tarryresidue may be separated from the circulating stream of liquid, saidtrap being indicated as preferably provided with the central bale 16having openings at its top and bottom and with a line 17 leading back tothe reaction chamber 2 for return of separated tar or aluminum `chloride to the reactionv chamber. The line-8, introducing part of the feedoil int-ol the system, preferably connects with the circulatr ing line10 between the trap 15 and heating coil 13.

The trap 15 operates as follows: The oil whichenters the trap risesupwardly through the trap and heats vthe baflie 16. This causes thetarry particles to be impounded against ,the baiiie while the liquidparticles flow -around`the batlle and out through the upper outlet ofthe trap. The tarry particles im- .pounded against the baille collectand drip back to the bottom of the trap and are forced throughl thelower opening` of the trap`b'aclc into the chamber 2.

The circulating line 10 is indicated as, terminatingwithin the reactionchamber 2 inv a pluralty of jet pipes 18 positioned near the bottom' ofthe reaction chamber and spaced apart throughout the bottom of thereaction chamber so that the oil entering the reaction chamber vfrom thecirculating line 10 is distributed through the reaction chamber in ,anumber of high velocity jets'. The 65 end 11of the circulating line'10is preferably connected within the still to a line 19 which leads to aposition under the yvapor line 6 and is there connected with a pan 20for catching reflux oils and feed oil lfrom the vapor line 6. The refluxtower 9 is indicated as connected with a vapor line 21 which leads to acondenser 22 from which a line 23 carries condensed oil to a receivingtank 24 for the rcduced low boiling point oil or naphtha. I aid receiver24 is indicated as provided wlth a valved gas vent 25 by which pressure,if desired, may be imposed upon the system. The tank 24 also may beconnected with a line 26 for discharge of the produced low boiling pointoil or naphtha. The reaction chamber 2 is also preferably provided Iwitha charger 27 by which anhydrous aluminumv chloride may be intermittentlyor continuously introduced into the reaction chamber 2 while the saidchamber is under pressure. For this purpose, the

charger 27 includes the two spaced apart valves 28 and 29, and thehopper 30. In certain cases, it may be desirable to introduce the.aluminum chloride continuously into the reaction chamber 2 in a liquidform, for example, by admixing the aluminum chloride with somehydrocarbon oil and for this purpose, thecharger 27 is indicated asconnected with a line 31. The reaction chamber 2 is also indicated aspreferably connected with a residual draw oif line 32connected with acooler 33 and hence to a resid.- uum tank 34 having the oil withdrawalline 35 and the tar withdrawal line 36.

The process as conducted in the apparatus thus describedl is preferablyas follows: In starting the apparatus, the hydrocarbon oil in properquantity s charged into the ieaction chamber 2 an is then circulatedfrom said reaction chamber 2 through circulatin line 10 and the heatinglzone back into sai chamber until the desired reaction temperature isreached. When the desired reaction temperature is reached, aluminumchloride 1.10 or equivalent metallic halide is added to the hydrocarbonoil and the process is then con tinued in a continuous manner bycontinuously or intermittently adding the requisite aluminum chlorideand continuously passing ,115 further fresh oil to the system.

While'the process may operate employing any desired hydrocarbon oil, anexample of a suitable oil responding particularly well to the process isgas oil fractions of petro- 120 leum oil such, for example, as have aBeaum gravity of 25c and derived from California or asphaltic base crudeoil.A The quantity of aluminum chloride added to the oil will varylargely with the character of oil to be r1,25 treated and thetemperature of treatment, and the character of product desired. Whendesiring to produce U. S. motor'grade gaso line from the' particular ilreferred to, I generally prefer to employ between 5 and 10 per 1130cent. by weight of aluminum chloride. The temperature of the `reactionmay also be varied through considerable range but is vapor line 6together with some higher boiling point oil and some aluminum chloride.

Said vapors are cooled within the dephlegmator 9 to a dischargetemperature suitable for condensing therefrom all fractions but thosedesirable in the finished naphtha. For this purpose, the dischargetemperature is enerall held between 300 and 360 F.

he coo g of the vapors is preferably accomplished by passing a ortionofthe feed oil through line 7 into t e uprising vapors whereby thecooling of the vapors also results in heatinglthis portion of the freshoil. This portion of the flux or condensed heavier oils pass through thevapor line 6 into the reaction chamber 2 andare there caught in the pan20 and part at least thereof/is circulated or recirculated from the bulksuppl `of materials within said chamber throug the heating coil 13 andback into said chamber. In the process, part of the bulksupply in thechamber 2 is circulated from the chamber to the line 10 and heating zoneback into the chamber, by reason of the fact thata part of the supply inchamber 2 is continuously vaporized and entrained with vapors passing'fout the line 6, where the dephlegmator 9 returns the same to the pan20, from whence it passes to the' line 10. Within the trap15 any portionof the aluminum chloride or tar in the circulating line 10 is separatedtherefrom and preferably continuously passed again to the reactionchamber 2. There is also added to the stream of materials beingcirculated in line the reaction chamber 2 thoroughly agitates andcommingles the hydrocarbon oil wlth the aluminum chloride, thusovercoming the agitation problems encountered in the normal" processes.

Preferably during the process, aluminum chloride residue is intimatelyor continuous'- ly withdrawn through line 32', passed through cooler 33,and hence into areceiver or reslduum tank 34. In said tank 34, any oilentrained in the residue is separated and eed oil together with anyrewithdrawn from line 35 while the residuum is withdrawn throughline 36.V

While the particular form of the invention herein described is welladapted to carry out the objects of the invention, numerousmodifications may be made and the invention is of the scope set forth inthe appended claims.

I claim:

1. A process of treatin hydrocarbon oil with anhydrous metallic alidewhich comprises maintaining a bulk supply of hydrocarbon oil andmetallic halide at a' conversion temperature and undergoin adecomposingreaction in a reaction cham r, passing the evolved vapors therefrom to arefiux tower, withdrawing reflux liquid from said reflux tower andcirculating a part of said liquid through a heating zone and back intosaid reaction chamber, separatin metallic halide sludge from thecirculatin uid and passing the metallic halide slu ge acl: into saidreaction chamber without passing through said heating zone.

2. An apparatus for treating hydrocarbon 'oils with anhydrous metallichalide in order ing from said reflux tower through 'a heating zone andback into said-reaction chamber, .a separator operative for separatingmetallic halide sludge from the liquid circulating in said line, and aby-pass line for passinv the metallic halide sludge thus separated ackinto said reaction chamber without passing through saidfheating zone. i

3. A process of 'treating hydrocarbon loils with metallic halide whichcomprises continuously maintaining a bulk' supply of hydrocarbonoil andmetallic halide at a c onversiontemperature, continuously passlngevolved vapors from said bulk supply to a reflux zone, continuouslycirculating reflux liquid from said reflux ,zon-e through a cleansingand separating zone to remove halide contained therein, and thenpassing. the cleansedliquid through Aa heating zone into said bulksupply, the liquid thus circulated ioa and cleansed being caused tocontinuously agitate said bulk supply, and continuously passing freshoil into said bulk supply while divertlnga portion of said oil to saidreflux tower.-

4. An apparatus for vtreating hydrocarbon oils with anhydrous metallicalide for 'decomposing the hydrocarbon oils into lower boiling pointoils, comprising a reaction chamber, a reflux tower operativelyconnected with said reactionchamber, a circulating'line leading fromsaid reux tower through a heating zone and back into Isaid reactionchamber, said vline terminatingin a plurality ofjetting means withinsaid reaction chamber whereb liquid from said line is caused to agitatet e contents of said reaction chamber, separating means for separatingmetallic hahde sludge from the liquid circulating.

in said line positioned in said line between -said reflux tower, aheating zone, and a bypass line for passing the metallic halide sludgethus separated back into said reaction chamber without passing throughsaid heating zone.

Signed at San Francisco, California, this 16th day of November, 1926.

RICHARD W. HANNA.

